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EU environmental law requires 30 ozone precursor volatile organic compounds (VOCs) to be measured for urban air quality control. In this study, 28 ozone precursor VOCs were measured at a rate of 0.5 Hz by an in-vehicle FTIR emission measurement system along with other VOCs. The vehicle used was a Euro 3 emission compliant diesel van. The test vehicle was started from a cold ambient temperature soak and driven under real world urban driving conditions. Diesel and B100 (100% Biodiesel) were compared using the same repeat journeys. The VOC emissions and OFP (ozone formation potential) were investigated as a function of engine warm up and ambient temperatures during cold start. The exhaust temperatures were measured along with the exhaust emissions. The temperature and duration of light off of the catalyst for VOC were monitored and showed a cold start period to catalyst light off that was considerably longer than would occur on the NEDC (New European Driving Cycle).